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1 The world leader in serving science
Ing. Roman Repáš
Emerging Markets Sales, EMEA, IC/SP
Thermo Fisher Scientific GmbH, Dreieich, Germany
Voda – čo všetko v sebe skrýva?
2
Agenda
• ISO methods for water analysis by Ion Chromatography
• Thermo Scientific Dionex Ion Chromatography systems and columns
for water analysis
• Speciation analysis of water by IC-ICP/MS
• Water analysis by IC-MS and IC-MS/MS
3 The world leader in serving science
ISO methods for water analysis by Ion Chromatography
4
Standardized IC-Methods for Water Analysis
• ISO 14911 - Water Quality
• Determination of dissolved lithium, sodium, ammonium, potassium, manganese(II),
calcium, magnesium, strontium and barium by ion chromatography - methods for water
and wastewater
• ISO 10304-1 –Water Quality
• Determination of dissolved anions by liquid chromatography of ions -- Part 1:
Determination of bromide, chloride, fluoride, nitrate, nitrite, phosphate and sulfate
• ISO 10304-3 – Water Quality
• Water quality - determination of dissolved anions by liquid chromatography (LC) - part 3:
Determination of chromate, iodide, sulfite, thiocyanate and thiosulfate in wastewater
5
Standardized IC-Methods for Water Analysis
• ISO 10304-4 – Water Quality
• Water quality - determination of dissolved anions by liquid chromatography (LC) -
part 4: Determination of chlorate, chloride and chlorite in slightly polluted wastewater
• ISO 15061 – Water Quality
• Determination of dissolved bromate in water
Comment: Preconcentration or direct injection – 10 µg/L Bromate
• ISO/DIS 11206 - Water Quality
• Determination of dissolved bromate — Method using ion chromatography (IC) and
post column reaction (PCR)
6
Working Ranges of the Analytical Method - ISO 14911
CationTypical Working Ranges
with 10 µL loop
[mg/L] 1)
Lithium 0,01 - 1
Sodium 0,10 - 10
Ammonium 0,10 - 10
Potassium 0,10 - 10
Manganese 0,50 - 50
Calcium 0,50 - 50
Magnesium 0,50 - 50
Strontium 0,50 - 50
Barium 1,00 - 100
1) The working range is limited by the ion-exchange capacity of the separator column. If necessary, the sample
shall be diluted to meet the working range, or use a 100 µL loop for lower working ranges.
7
ISO 10304-1 – News
• This second edition of ISO 10304-1 cancels and replaces ISO 10304-1:1992
and ISO 10304-2:1995.
• One method for water, e.g. drinking water, ground water, surface water, waste water, leachates
and marine water.
• Isocratic AND Gradient Elution
• Carbonate/Bicarbonate AND Hydroxide Eluents (e.g. KOH)
• Only Examples for Suppressed Conductivity Compatible Eluents
• Mode of Calibration: Customer‘s Choice (Linear, Quadratic…)
• AND:
• Minimum Requirement for the Separation: R ≥ 1.3 for Neighboring Peaks
The User Decides on Application, Mode of Calibration, and Mode of Elution !!
8
Examined Working Range of the Analytical Method – ISO 10304-1
Anion Examined Working Range
mg/L
Bromide 0,1 to 1 to 1 to 10
Chloride 0,5 to 5 to 5 to 50
Fluoride 0,02 to 0,2 to 0,5 to 5
Nitrate 0,5 to 5 to 10 to 100
Nitrite 0,1 to 1 to 1 to 10
Orthophosphate 0,5 to 5 to 10 to 100
Sulfate 1 to 10 to 10 to 100
9 The world leader in serving science
Thermo Scientific Dionex Ion Chromatography systems and columns for water analysis
10
The Thermo Scientific Dionex Ion Chromatography Systems
RFIC
HPIC
Dionex Aquion Dionex Integrion Dionex ICS-4000 Dionex ICS-6000
11
IC Autosamplers
Thermo Scientific Dionex
AS-DV Autosampler
Entry Level
• Carousel Type
• 50 x 5 mL PolyVials
• 50 x 0.5 mL PolyVials
• Filter Caps
• Full Loop, Concentrator
• Simultaneous Injection
• Optional 6-port/10-port Valve
Thermo Scientific Dionex
AS-HV Autosampler
High Volume
• X0Z-Type
• 24 x 250 mL TCF
• 15 x 250 mL Bottles
• Full Loop Injection, Concentrator Loading
• Simultaneous Injection
• Peristaltic Pump for sample loading and Needle Port Rinse
Thermo Scientific Dionex
AS-AP Autosampler
For IC, BioIC, and Cap IC
• Carousel-Type
• 81 x 10 mL Vials
• 120 x 1.5 mL or 0.3 mL Vials
• 3 x 96 Well Plates
• 3 x 384 Well Plates
• Full/Partial Loop, Limited Sample, Concentrator Loading
• Push and Pull Loop injection
• Tray Thermostat
• Optional Injection Valve
• Optional Diverter Valve
• Optional Fractionation valve
• Sequential Injection
• Simultaneous Injection
• Autodilution
12
Municipal Drinking Water Analysis
Municipal Drinking Water Analysis by Fast ICAB120
Municipal Drinking Water Conditions
7
0 4Minutes
µS
10
1 32 5-0.5
2
1 543 6
Columns: Dionex IonPac AG22-Fast-4µm
Dionex IonPac AS22-Fast-4µm,
2 150 mm
Eluent: 4.5 mM Sodium Carbonate
1.4 mM Sodium Bicarbonate
Flow Rate: 0.5 mL/min
Inj. Volume: 2.5 µL
Column Temp.: 30 C
Detection: Suppressed conductivity,
Dionex AERS 500 Carbonate, 2 mm
17 mA, recycle mode
Peaks:
1. Fluoride < 1 5. Nitrate 1.0 mg/L
2. Chloride 120 6. Phosphate < 2
3. Nitrite < 1 7. Sulfate 56
4. Bromide < 1
13
Determination of Inorganic Anions in Environmental Waters Using a Hydroxide-Selective Column
AN154 and Update
with Dionex IonPac
AS18-4µm column
Water analysis
Municipal Wastewater Sample Conditions
Columns: Dionex IonPac AG18-Fast-4µm
Dionex IonPac AS18-Fast-4µm,
4 150 mm
KOH Gradient: 15–44 mM (0.2 to 6 min)
Eluent Source: Dionex EGC 500 cartridge with Dionex
CR-ATC 600 trap and Dionex high
pressure degasser devices
Flow Rate: 1 mL/min
Inj. Volume: 10 µL
Column Temp.: 30 C
Detection: Suppressed conductivity, Dionex
AERS 500, 4 mm, 109 mA, recycle
Sample Prep.: 5x dilution with deionized water
Peaks:
1. Fluoride 1.0 5. Sulfate 51.8 mg/L
2. Chloride 90.6 6. Nitrate 2.6
3. Nitrite 1.0 7. Phosphate 0.36
4. Carbonate --
7
0 6
Minutes
µS
90
3 9-10
2
1 643
5
14
0 5 10 15 20 25 30-0.1
0.3
µS
679 10
23
4 5 8 111
–50
500
µS
0 5 10 15 20 25 30Minutes
11
4
81 67 95
Determination of Trace Bromate Using IonPac AS23
Columns: Dionex IonPac AG23, AS23, 4 mm
Eluents: 4.5 mM Sodium carbonate/
0.8 mM Sodium bicarbonate
Temperature: 30 C
Flow Rate: 1.0 mL/min
Inj. Volume: 200 µL
Detection: Suppressed conductivity,
Dionex ASRS, 4 mm,
AutoSuppression™,
external water mode
Peaks: 1. Fluoride 1.0 mg/L (ppm)
2. Chlorite 0.01
3. Bromate 0.005
4. Chloride 50
5. Nitrite 0.1
6. Chlorate 0.01
7. Bromide 0.01
8. Nitrate 10
9. Carbonate 50
10. Phosphate 0.1
11. Sulfate 50
LOD
(µg/L)
1.63
Recommended carbonate column for EPA Method 300.0 (B)
15
Determination of Trace Bromate Using IonPac AS19-4µm column
System: Thermo Scientific™ Dionex™
ICS-5000+ HPIC system
Column: Thermo Scientific™ Dionex™
IonPac™ AS19-4µm + guard
(4 250 mm)
Eluent : 10 mM KOH from 0 to 10 min,
10–45 mM KOH from 10 to 25 min
Eluent Source: Thermo Scientific™ Dionex™
EGC 500 KOH Cartridge
Flow Rate: 1.0 mL/min
Inj. Volume: 200 µL
Temperature: 30 ˚C
Detection: Suppressed Conductivity,
Thermo Scientific™ Dionex™
AERS™ 500 suppressor, 4 mm
AutoSuppression, recycle mode
Sample: Simulated Drinking Water
Peaks: 1. Fluoride 1.0 mg/L
2. Chlorite 0.005
3. Bromate 0.005
4. Chloride 50.0
5. Nitrite 0.005
6. Chlorate 0.005
7. Bromide 0.005
8. Nitrate 10.0
9. Carbonate 25.0
10. Sulfate 50.0
11. Phosphate 0.20
-0.2
0
0.5
µS
1
23
4
5 67
8 9 10 11
0 8 16 24 32-50
500
µS
Minutes
123
4
5 678
9
10
11
LOD
(µg/L)
0.32
Recommended hydroxide column for EPA Method 300.0 (B)
16
System Configuration - ISO 11206 for trace bromate analysis
Eluent
Autosampler
ICS Guard Separator
PC10 /
ICS Pump
Mixing
Tee
Absorbance
Detector
Knitted RX Coil
Ambient Temp.
Effluent to waste
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Bromate Determination with Acidic Eluent - ISO 11206
Column: Thermo Scientific™
Dionex™ CarboPac™ PA1
(4 250 mm)
Eluent: 200 mmol/L MSA
Flow: 1 mL/min
Injection vol.: 500 µL
Detection: UV 352 nm (after PCR)
Temperature: 30 °C
PCR:
Solution A: 0.27 mol/L KI, 0.05 mmol/L
(NH4)6Mo7O24 · 4H2O
Flow 0.3 mL/min
Reaction coil: 375 µL
Bromate 1.2 µg/L
Reaction at Ambient Temp., and no Interferences from Chlorite
0.0 2.0 4.0 6.0 8.0 10.0
-5.0
-2.5
0.0
2.5
5.0
Bromate
mAU
LOD
(µg/L)
LOQ
(µg/L)
0.07 0.22
Minutes
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Eluent
Autosampler
High-Pressure
Nonmetallic
Pump
IonPac® NG1 IonPac AS7
PC10 PCR
Reservoir
System Configuration for Hexavalent Chromium by EPA Method 218.6
Mixing
Tee
UV-Vis
Detector
Knitted Reaction Coil
Waste
Sample Loop
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Determination of Cr(VI) in Drinking Water Using Optimized EPA Method 218.6
Column: IonPac® NG1, AS7
Eluent: 250 mM (NH4)2 SO4
100 mM NH4OH
Flow: 1.0 mL/min
Inj. Volume: 1000 mL
Postcolumn 2 mM Diphenylcarbazide
Reagent: 10% CH3OH
1N H2SO4
0.33 mL/min
Reaction Coil: 750 mL
Detector: UV-Vis (530 nm)
Sample: Sunnyvale, CA tap water
MDL = 0.02 ppb
00 2 4 6 8
Cr(VI)
AU
min
0.055 µg/L
20
Column: IonPac AS7
Eluent: 0.5 M Sodium acetate0.1 M Sodium hydroxide0.5 % (v/v) Ethylenediamine
Flow Rate:1 mL/min
Detector: ED40, silver working electrode,0.00 V vs. Ag/AgCl reference
Peaks: Matrix 1 Matrix 21. S2–1000 ppb 3. S2– 25ppb2. CN–100 ppb 4. CN–125 ppb
Matrix 1: 1 M
NaOH
Matrix 2: Alkaline
Absorber
(Wastewater)
0 2 4 6 8 Minutes
3
4
0 2 4 6 8
2
1
Determination of Cyanide and Sulfide in Sodium Hydroxide and Waste Water Samples Using the IonPac® AS7 Column with Amperometric Detection
21 Proprietary & Confidential
Fast Cation Separations with CS12A 5-µm 3 x 150 mm
Temperature: 30 C
Eluent: A. 33 mM Methanesulfonic acid
B. 20 mM Methanesulfonic acid
Flow Rate: A. 0.8 mL/min
B. 1.0 mL/min
Inj. Volume: 25 µL
Detection: Suppressed conductivity,
CSRS® ULTRA 2 mm,
AutoSuppression® recycle
mode
Peaks: 1. Lithium
2. Sodium
3. Ammonium
4. Potassium
5. Rubidium
6. Cesium
7. Magnesium
8. Calcium
9. Strontium
10. Barium
0 20
6.5
12
3
47 8
0 2 4 6 8 10 Minutes0
4.6
1
2
34
5
6
78
9
10
31
A
B
1564
0
µS
µS
22 Proprietary & Confidential
Columns: IonPac® CG5A, CS5A, 2mm
Eluent: MetPac™ PDCA
Eluent Flow Rate: 0.3 mL/min
Post Column Reagent: PAR in MetPac postcolumn
reagent diluent
PCR Flow Rate: 0.15 mL/min
Column Temp: 30 °C
Injection Volume: 1000 µL
Detection: 530 nm, 10 mm cell
Peaks: 1. Iron 2 µg/L
2. Copper 1
3. Nickel 2
4. Zinc >2
5. Cobalt 1
6. Cadmium 5
7. Manganese3
8. Iron 2
Large Sample Loop Injection of µg/L Levels of Transition Metalsin a 2-mm System with Pneumatic Postcolumn Delivery
0 2 4 6 8 10 12 14 Minutes
–5.00x10–3
2.00x10–2
4
2.00x10–2
–5.00x10–3
2
3
1
4
5
6
78
Blank
AU
AU
23
Advantages of Ion Chromatography in Water Analysis
• High Specificity & Selectivity
• Standardized Methods (ISO & Local Standards)
• Multiple Components
• High Degree of Automation
• Simple & Complex Matrices
• Easily Upgradable
• Multiple Option (Detectors, Columns, Iso/Grad)
24 The world leader in serving science
Speciation analysis of water by IC-ICP/MS
25
Speciation with IC-ICP-MS
• Very simple hardware connection:
• Simple interchange between standard ICP-MS
analysis and IC-ICP-MS
• No need to turn off plasma
• Dionex IC systems are entirely metal-free
(PEEK)
• Fully integrated systems with Chromeleon
plug-in for Qtegra enables seamless control
of both units
• Powerful separation chemistries with a wide
selection of columns also for specialized
applications
• Reagent-Free Ion Chromatography (RFIC)
for ease of use
• IC-ICP-MS is the ideal choice for trace
elemental speciation because:
26
The IC-ICP-MS Bundles
IC Pump Channels Autosampler Column heater RFIC Elution possibilities Applications
ICS-6000 Quaternary AS-AP ✓ optional Gradient - full flexibility As, Br, Cr, Fe, Hg, I, Se, Sn
27
Cr-Species – Anion Exchange & ICP/MS
0.00 1.00 2.00 3.00
0
1,250
2,500
3,750
5,000
6,250
7,500
9,000Bremen #2 1 ppb Cr_id_21 Trace__52Cr_SG_021_004
[cps]
min
Cr(III)
Cr(VI)Column: Thermo Scientific Dionex
IonPac AG7, 2 x 50 mm Eluent: 0.4 mL/min
Eluent: 60 mmol/L HNO3, pH 2 with NH4OH
Injection vol.: 100 µL
Runtime: 3.5 min
Analytes: Cr(III) und Cr(VI) je 1 µg/L
…
28
IC-ICP-MS: Cr(III) and Cr(VI) Calibrations
29
Cr in Drinking Water: Thermo Scientific AN 43098
42.5 ng/L
30
IC-ICP-MS for As Speciation
• 6 Species determined
• ~7000 cps / ppb
• ~15 Min. Runtime
• Anion Exchange:
• Thermo Scientific Dionex IonPac AS7 (2x250mm)
• Gradient-Elution
• 20-200 mmol/L Ammonium carbonate
• Flow: 0.3 mL∙min-1
• Injectionvol.: 20 µL
31 The world leader in serving science
Water Analysis by IC-MS and IC-MS/MS
32
Analysis of Halo Acetic Acids (HAAs) by IC-MS/MS and IC-MS
33
IC-MS/MS for HAAs diagram
High-Pressure NonmetallicPump
Eluent Generator
(OH–)
Waste
Sample Inject(Autosampler)
CR-TC
Electrolytic Eluent
Suppressor
Separator ColumnIonPac AS 31
TSQ MS
Conductivity Detector
0.31 µS
Data Management
Makeup Pump(MeCN or IPA)
MD
Valve
Waste
34
Analysis of Haloacetic Acids in Municipal Drinking Water on Dionex IonPac AS31
Column: Dionex IonPac AG31/AS31, 2mm
Temperature: 15 ˚C
Eluent: KOH (EG)
Gradient 17 mmol/L from 0 to 7 min, 17‒85 mmol/L from
7 to 18 min, 85 mmol/L from 18 to 35 min
Flow rate: 0.30 mL/min
Inj. volume: 100 µL
Detection: Suppressed conductivity,
AutoSuppression, recycle mode
Sample Municipal Drinking Water Spiked with 9HAAs
Peaks (Standard): 1. Fluoride NQ
in mg/L 2. Unknown NQ
3. Monochloroacetate 0.5
4. Monobromoacetate 0.5
5. Chloride NQ
6. Sulfate+carbonate NQ
7. Dichloroacetate 0.5
8. Unknown NQ
9. Bromochloroacetate 0.5
10. Unknown NQ
11. Dibromoacetate 0.5
12. Chlorate NQ
13. Bromide NQ
14. Nitrate NQ
15. Trichloroacetate 0.5
16. Bromodichloroacetate 0.5
17. Chlorodibromoacetate 0.5
18. Tribromoacetate 0.5 NQ: Not Quantified
35
Analysis of Haloacetic Acids in Municipal Drinking Water on Dionex IonPac AS31
Municipal Drinking Water
Municipal Drinking Water
Spiked with 0.5 mg/L of 9 HAAs
0 5 10 15 20 25 30 35 40
-0.5
5.0 1
2
3
4
5+6
7
8 9
10 11
12 13
14
15 16 17 18
Minutes
µS
-0.5
5.01
2
5+6
8 10 12 13
14µS
36
Water sample with and without spiking with 10 μg/L of 9 HAAs, Bromate and DALAPON
37
Detection Limits for HAAs, Bromate & DALAPON
MDL (µg/L, n=7) AbbreviationEPA 557
Calculated DL GC-ECD AS24 Calculated DL AS31 Calculated DL IC X IC (2D IC) IC-MS
Monochloroacetic acid MCAA 0.2 0.273 0.105 0.19 0.085 0.1
Monobromoacetic acid MBAA 0.064 0.204 0.104 0.021 0.1 0.03
Bromate Bromate 0.02 N.D 0.059 0.014 0.12
Dalapon Dalapon 0.038 N.D 0.05 0.079 0.12
Dichloroacetic acid DCAA 0.055 0.242 0.044 0.019 0.41 0.033
Bromochloroacetic acid BCAA 0.11 0.251 0.059 0.086 0.3 0.16
Dibromoacetic acid DBAA 0.015 0.066 0.021 0.009 0.09 0.16
Trichloroacetic acid (163/119) TCAA 0.09 0.079 0.033 0.073 0.26 0.67
Bromodichloroacetic acid BDCAA 0.05 0.091 0.141 0.087 0.29 2.79
Chlorodibromoacetic acid DBCAA 0.041 0.468 0.214 0.19 0.055 1.04
Tribromoacetic acid TBAA 0.067 0.82 0.159 0.067 0.28 4.55
IC – ESI MS/MS
38
Suppressed ion chromatography with MS-MS detection
• Advantages
• Direct injection method with matrix diversion
• Eliminates liquid-liquid extraction, derivatization and separation
• Eliminates co-elution issues because MS is a selective detector
• MS/MS provides confirmation information
• Fully automated
• Recovery > 90%
IC-MS/MS Method for HAAs
39
Determination of HAAs, Bromate and Dalapon in Drinking Water using IC-MS with IonPac AS31, 2 mm
40
IC-MS Schematics
41
Summary of method performance and comparison with MDL to U.S. EPA Method 557
Abbreviation Retention Time US EPA 557 DL MDLCalibration Range
(μg/L)r2-value
MCAA * 6.5 0.2 0.1 0.1–100 0.999
MBAA * 7.2 0.06 0.03 0.1–100 0.998
Bromate 7.7 0.02 0.12 0.5–100 0.998
Dalapon 12.3 0.04 0.12 0.5–100 0.999
DCAA * 13.4 0.06 0.03 0.1–100 0.998
BCAA 15 0.11 0.16 0.5–100 0.998
DBAA * 17.1 0.02 0.16 0.5–100 0.999
TCAA * 24.8 0.09 0.67 1–100 0.999
BDCAA 27 0.05 2.79 4–100 0.998
DBCAA 30.4 0.04 1.04 4–100 1
TBAA 35.1 0.07 4.55 10–100 1
42
Summary of IC-MS method for the determination of HAAs
• IC-MS method is fast (40 min vs. 60 min in U.S. EPA Method 557)
and linear for 11 analytes with an r2 value range of 0.998 to 1.
• The method meets the sensitivity for the determination of U.S. EPA regulated HAA5,
but its not regulated yet.
• Typically, the method is sensitive for the determination of not yet regulated HAAs
(BCAA, BDCAA, CDBAA, TBAA ).
43
Thank You – Any Questions?
?
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